WO2017158994A1 - Composition adhésive de type film, adhésif de type film, procédé de production d'adhésif de type film, emballage de semi-conducteur utilisant l'adhésif de type film, et procédé de production associé - Google Patents

Composition adhésive de type film, adhésif de type film, procédé de production d'adhésif de type film, emballage de semi-conducteur utilisant l'adhésif de type film, et procédé de production associé Download PDF

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Publication number
WO2017158994A1
WO2017158994A1 PCT/JP2016/089006 JP2016089006W WO2017158994A1 WO 2017158994 A1 WO2017158994 A1 WO 2017158994A1 JP 2016089006 W JP2016089006 W JP 2016089006W WO 2017158994 A1 WO2017158994 A1 WO 2017158994A1
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Prior art keywords
film
adhesive
aluminum nitride
film adhesive
epoxy resin
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PCT/JP2016/089006
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English (en)
Japanese (ja)
Inventor
稔 森田
切替　徳之
佐野　透
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古河電気工業株式会社
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Application filed by 古河電気工業株式会社 filed Critical 古河電気工業株式会社
Priority to JP2017518584A priority Critical patent/JP6868555B2/ja
Priority to KR1020177022011A priority patent/KR102042516B1/ko
Priority to CN201680017697.0A priority patent/CN107406742B/zh
Publication of WO2017158994A1 publication Critical patent/WO2017158994A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67132—Apparatus for placing on an insulating substrate, e.g. tape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27—Manufacturing methods
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32135—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
    • H01L2224/32145—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being stacked
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Definitions

  • the present invention relates to a composition for film adhesive having high thermal conductivity, a film adhesive, a method for producing a film adhesive, a semiconductor package using the film adhesive, and a method for producing the same.
  • the components of the semiconductor package are required to have thermal conductivity that allows the generated heat to escape to the outside of the package.
  • a so-called die attach material that joins between a semiconductor element and a wiring substrate or between semiconductor elements is required to have high thermal conductivity and sufficient insulation and adhesion reliability.
  • the entrained air not only lowers the adhesive strength after heat curing of the die attach film, but also causes package cracks. Therefore, in order to suppress an increase in melt viscosity, it is necessary to reduce the filling amount as much as possible to achieve high thermal conductivity, and it is necessary to select a filler having higher thermal conductivity.
  • the wear rate of the processing blade by the die attach film is small in the so-called dicing process of simultaneously cutting the die attach film and the semiconductor wafer on which the semiconductor element is formed.
  • the wear rate of the processing blade by the die attach film increases, and although the predetermined cutting can be performed for a while after the start of the cutting process (dicing process), the cutting amount of the die attach film gradually increases. It becomes insufficient.
  • the frequency of blade replacement is increased in order to prevent this problem from occurring, the productivity will decrease, leading to an increase in cost.
  • the wafer may be chipped. This causes chipping and the like, resulting in a decrease in yield.
  • a metal wire is used from a conventionally used gold material to a copper wire.
  • a copper material having a lower electrical resistance than the conventionally used aluminum material is used as the semiconductor element circuit material.
  • a die attach film is bonded on such a copper semiconductor member, it is necessary that the semiconductor package is not corroded during a reliability test such as a biased HAST (Highly Accelerated Stress Test) under high temperature and high humidity. is there. For this reason, it is necessary for the die attach film to have a small amount of ionic impurities.
  • the high thermal conductivity die attach film has i) low melt viscosity for developing adhesion, ii) blade abrasion resistance in the dicing process, and iii) low ion for preventing corrosion of the copper semiconductor member. Impurity characteristics are required.
  • Examples of materials that can be used as the high thermal conductivity die attach film include, for example, Patent Document 1, an epoxy resin, a polymer component having a glass transition temperature of 95 ° C. or higher, a polymer component having a glass transition temperature of ⁇ 30 ° C. or lower, and a thermal conductivity of 10 W.
  • Patent Document 1 an epoxy resin, a polymer component having a glass transition temperature of 95 ° C. or higher, a polymer component having a glass transition temperature of ⁇ 30 ° C. or lower, and a thermal conductivity of 10 W.
  • a highly heat-conductive adhesive sheet composed of an inorganic filler of at least / m ⁇ K has been proposed.
  • Patent Document 1 although it has thermal conductivity and low melt viscosity, it uses high-hardness aluminum oxide and has blade wear resistance. It can be estimated that problems remain, and studies on ionic impurities were insufficient.
  • Patent Document 2 proposes a high thermal conductive resin composition containing high thermal conductive particles, an epoxy resin having mesogen and a high molecular weight component.
  • the high thermal conductive resin composition described in Patent Document 2 although it has high thermal conductivity and adhesion, it can be estimated that a high hardness aluminum oxide is used, and the problem of blade wear resistance remains, In addition, studies on ionic impurities were insufficient.
  • Patent Document 3 proposes a heat conductive filler made of aluminum hydroxide and silicon dioxide and a sheet of a heat conductive member made of a silicon-based resin.
  • the sheet of the heat conducting member described in Patent Document 3 although it has a certain degree of high heat conductivity, there is still a problem with the adhesion to the adherend, and ionic impurities. The examination of was also insufficient.
  • the present invention has been made in view of the above-described problems of the prior art, and has excellent adhesion to an adherend, a sufficiently low wear rate of a processing blade, and does not corrode a copper semiconductor member.
  • Film adhesive composition capable of obtaining a film adhesive that retains low ionic impurity properties and exhibits excellent thermal conductivity after thermosetting, a film adhesive, a method for producing a film adhesive, It is an object of the present invention to provide a semiconductor package using a film adhesive and a method for manufacturing the same.
  • a composition for film adhesive containing an epoxy resin (A), an epoxy resin curing agent (B), a phenoxy resin (C) and an aluminum nitride filler (D),
  • the content of the aluminum nitride filler (D) is based on the total amount of the epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C), and the aluminum nitride filler (D). 30-60% by volume,
  • the film adhesive obtained from the film adhesive composition is heated from 25 ° C.
  • the aluminum nitride filler (D) is characterized in that a surface oxidation layer is applied to the surface of the filler and a water-resistant surface treatment with phosphoric acid or a phosphoric acid compound is performed ( The composition for film adhesives as described in 1).
  • an ion trapping agent selected from a triazine thiol compound, a zirconium-based compound, an antimony bismuth-based compound and a magnesium aluminum-based compound is added in an amount of 1.0 to 3.0 mass with respect to the aluminum nitride filler (D).
  • the composition for film adhesive according to any one of the above (1) to (3) is produced by coating and drying on a release-treated base film.
  • Manufacturing method of film adhesive (6) a first step of providing an adhesive layer by thermocompression bonding the film adhesive and dicing tape according to (4) on the back surface of the semiconductor wafer having at least one semiconductor circuit formed on the front surface; A second step of obtaining a semiconductor chip with an adhesive layer comprising the semiconductor wafer and the adhesive layer by simultaneously dicing the semiconductor wafer and the adhesive layer; A third step of detaching the dicing tape from the adhesive layer, and thermocompression bonding the semiconductor chip with the adhesive layer and the wiring board through the adhesive layer; and A fourth step of thermosetting the adhesive layer;
  • a method for manufacturing a semiconductor package comprising: (7) A semiconductor package obtained by the manufacturing method according to (6).
  • the adhesion with the adherend is excellent, the wear rate of the processing blade is sufficiently small, and the low ionic impurity property is maintained so as not to corrode the copper semiconductor member, and it is excellent after thermosetting.
  • Film adhesive composition capable of obtaining a highly thermally conductive film adhesive exhibiting thermal conductivity, film adhesive, film adhesive manufacturing method, semiconductor package using film adhesive, and The manufacturing method can be provided.
  • FIG. 1 is a schematic longitudinal sectional view showing a preferred embodiment of the first step of the method for manufacturing a semiconductor package of the present invention.
  • FIG. 2 is a schematic longitudinal sectional view showing a preferred embodiment of the second step of the method for manufacturing a semiconductor package of the present invention.
  • FIG. 3 is a schematic longitudinal sectional view showing a preferred embodiment of the third step of the method for manufacturing a semiconductor package of the present invention.
  • FIG. 4 is a schematic longitudinal sectional view showing a preferred embodiment of a process for connecting bonding wires in the method of manufacturing a semiconductor package of the present invention.
  • FIG. 5 is a schematic longitudinal sectional view showing a multi-layered embodiment of the semiconductor package manufacturing method of the present invention.
  • FIG. 6 is a schematic longitudinal sectional view showing another multi-layered embodiment of the semiconductor package manufacturing method of the present invention.
  • FIG. 7 is a schematic longitudinal sectional view showing a preferred embodiment of a semiconductor package manufactured by the method for manufacturing a semiconductor package of the present invention.
  • the composition for a film adhesive of the present invention (hereinafter referred to as a composition for a high thermal conductive film adhesive) includes an epoxy resin (A), an epoxy resin curing agent (B), a phenoxy resin (C), and aluminum nitride. Each contains a filler (D), and the content of the aluminum nitride filler (D) contains the epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C), and the aluminum nitride filling. 30 to 60% by volume based on the total amount of the agent (D). Further, the high thermal conductive film adhesive obtained by the composition for high thermal conductive film adhesive of the present invention has a temperature of 200 at 80 ° C.
  • the minimum melt viscosity of the high thermal conductive film adhesive obtained with the composition for high thermal conductive film adhesive of the present invention is 80 ° C. or higher when the temperature is increased from 25 ° C. at a rate of 5 ° C./min. Reaches a minimum melt viscosity in the range of 200 to 10,000 Pa ⁇ s.
  • the minimum melt viscosity is preferably in the range of 200 to 3000 Pa ⁇ s, particularly preferably in the range of 200 to 2000 Pa ⁇ s. When the melt viscosity is larger than this range, voids are likely to remain between the wiring substrate irregularities when the semiconductor chip provided with the film adhesive is thermocompression bonded onto the wiring substrate.
  • the melt viscosity is a rheometer (trade name: RS6000, manufactured by Haake Co., Ltd.), and a change in viscosity resistance at a temperature range of 25 to 200 ° C. and a heating rate of 5 ° C./min is measured.
  • the viscosity resistance when the temperature is 80 ° C. or higher in the obtained temperature-viscosity resistance curve.
  • the epoxy resin (A), the epoxy resin curing agent, etc. In order to set the minimum melt viscosity within the above range, in addition to the content of the aluminum nitride filler (D), and the type of the aluminum nitride filler (D), the epoxy resin (A), the epoxy resin curing agent, etc. It can be adjusted according to the kind of the coexisting compound or resin and the content thereof.
  • the high thermal conductivity film adhesive of the present invention has a thermal conductivity of 1.0 W / m ⁇ K or more after thermosetting.
  • the thermal conductivity is preferably 1.5 W / m ⁇ K or more. If the thermal conductivity is less than the above lower limit, the generated heat tends to be difficult to escape to the outside of the package. Since the high thermal conductive film adhesive of the present invention exhibits such excellent thermal conductivity after thermosetting, the high thermal conductive film adhesive of the present invention is adhered to an adherend such as a semiconductor wafer or a wiring board. By heat-curing, heat dissipation efficiency to the outside of the semiconductor package is improved.
  • the upper limit of the thermal conductivity is not particularly limited, but is practically 5.0 W / m ⁇ K or less.
  • the thermal conductivity of the film-like adhesive after thermosetting is a heat flow meter using a thermal conductivity measuring device (trade name: HC-110, manufactured by Eihiro Seiki Co., Ltd.).
  • HC-110 manufactured by Eihiro Seiki Co., Ltd.
  • a value obtained by measuring the thermal conductivity by the method (conforming to JIS-A1412).
  • the epoxy resin (A) in addition to the content of the aluminum nitride filler (D) and the type of the aluminum nitride filler (D), the epoxy resin (A), the epoxy resin curing agent, etc. It can be adjusted according to the kind of the coexisting compound or resin and the content thereof.
  • the high thermal conductive film adhesive of the present invention has an electric conductivity of 50 ⁇ S / cm or less of extracted water extracted into pure water at 121 ° C. for 20 hours after thermosetting.
  • the electric conductivity is preferably 40 ⁇ S / cm or less. If the electrical conductivity exceeds the above upper limit, the copper material tends to be corroded during a reliability test such as bias HAST under high temperature and high humidity of the semiconductor package.
  • the lower limit of the electrical conductivity is not particularly limited, but is practically 0.1 ⁇ S / cm or more.
  • the electric conductivity refers to an electric conductivity meter (trade name: AE) obtained by placing the heat-cured film adhesive in pure water and extracting it at 121 ° C. for 20 hours.
  • the electrical conductivity can be adjusted to the above range by using a surface-modified aluminum nitride filler (D) or a phosphate ester-based surfactant or an ion trapping agent (ion trapping agent) as an additive. .
  • the epoxy resin (A) contained in the composition for high thermal conductive film adhesive of the present invention may be any of liquid, solid or semi-solid.
  • the term “liquid” means that the softening point is less than 50 ° C.
  • the term “solid” means that the softening point is 60 ° C. or higher
  • the term “semi-solid” means that the softening point is that of the above-mentioned liquid Is between the softening point of (50 ° C. or more and less than 60 ° C.).
  • the epoxy resin (A) used in the present invention has a softening point of 100 ° C.
  • the softening point is a value measured by a softening point test (ring-and-ball type) method (measuring condition: conforming to JIS-2817).
  • the crosslink density of the cured body is increased, and as a result, the contact probability between the mixed aluminum nitride fillers (D) is high and the contact area is widened, so that the heat is higher.
  • the epoxy equivalent is preferably 500 g / eq or less, more preferably 150 to 450 g / eq.
  • an epoxy equivalent means the gram number (g / eq) of resin containing an epoxy group of 1 gram equivalent.
  • phenol novolak type As the skeleton of the epoxy resin (A), phenol novolak type, orthocresol novolak type, cresol novolak type, dicyclopentadiene type, biphenyl type, fluorene bisphenol type, triazine type, naphthol type, naphthalenediol type, triphenylmethane type, Examples include tetraphenyl type, bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, and trimethylolmethane type.
  • the triphenylmethane type, the bisphenol A type, the cresol novolak type, and the orthocresol novolak type are preferable from the viewpoint of obtaining a film adhesive having a low resin crystallinity and a good appearance.
  • the content of the epoxy resin (A) is preferably from 3 to 30% by mass, more preferably from 5 to 25% by mass, based on the total mass of the composition for high thermal conductive film adhesive of the present invention.
  • the content is less than the above lower limit, since the resin component that increases the crosslink density when cured, the thermal conductivity of the film adhesive tends to be difficult to improve, and on the other hand, when the content exceeds the above upper limit. Since the main component is an oligomer, the film state (film tackiness and the like) tends to change easily even with a slight temperature change.
  • Epoxy resin curing agent (B) As the epoxy resin curing agent (B) contained in the highly heat conductive film adhesive composition of the present invention, known curing agents such as amines, acid anhydrides and polyhydric phenols can be used. .
  • the epoxy resin (A) and the phenoxy resin (C) have a low melt viscosity, exhibit curability at a high temperature exceeding a certain temperature, have fast curability, and further store at room temperature for a long time. It is preferable to use a latent curing agent from the viewpoint that a composition for film adhesive with high storage stability that can be obtained is obtained.
  • latent curing agents dicyandiamides, imidazoles, curing catalyst composite polyhydric phenols, hydrazides, boron trifluoride-amine complexes, amine imides, polyamine salts, modified products thereof and microcapsule typecan be mentioned.
  • polyhydric phenols are used.
  • curing catalyst composite type polyhydric phenols examples include novolak type phenol resins, phenol aralkyl type phenol resins, polyvinyl type phenol resins, and resol type phenol resins. These may be used alone or in combination of two or more.
  • the content of the epoxy resin curing agent (B) is preferably 0.5 to 100% by mass and more preferably 1 to 80% by mass with respect to the epoxy resin (A). If the content is less than the above lower limit, the curing time tends to be longer. On the other hand, if the upper limit is exceeded, excess curing agent remains in the film adhesive, and the residual curing agent adsorbs moisture. There is a tendency that defects are likely to occur in a reliability test after the adhesive is incorporated into a semiconductor.
  • the phenoxy resin (C) contained in the highly heat conductive film adhesive composition of the present invention is used for imparting sufficient adhesion and film forming property (film forming property) to the film forming layer.
  • Phenoxy resin has good compatibility with epoxy resin because of its similar structure, low resin melt viscosity, and good adhesion.
  • the phenoxy resin is obtained from bisphenol such as bisphenol A and epichlorohydrin.
  • a thermoplastic resin having a mass average molecular weight of 10,000 or more is preferable. Mixing the phenoxy resin is effective in eliminating tackiness and brittleness at room temperature.
  • Preferred phenoxy resins include bisphenol A type, bisphenol A / F type, bisphenol F type, and cardo skeleton type phenoxy resins.
  • Phenoxy resins are 1256 (trade name: bisphenol A type phenoxy resin, manufactured by Mitsubishi Chemical Corporation), YP-70 (trade name: bisphenol A / F type phenoxy resin, manufactured by Nippon Kayaku Epoxy Manufacturing Co., Ltd.), FX -316 (trade name: Bisphenol F-type phenoxy resin, manufactured by Nippon Kayaku Epoxy Co., Ltd.), FX-280S (trade name: cardo skeleton type phenoxy resin, manufactured by Nikka Chemical Epoxy Manufacturing Co., Ltd.), etc.
  • a commercially available phenoxy resin may be used.
  • the mass average molecular weight is a value determined in terms of polystyrene by GPC (Gel Permeation Chromatography).
  • the glass transition temperature (Tg) of the phenoxy resin is preferably less than 100 ° C, and more preferably less than 80 ° C.
  • the lower limit of the glass transition temperature (Tg) is preferably 0 ° C. or higher, and more preferably 10 ° C. or higher.
  • the content of the phenoxy resin is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and further preferably 4 to 13% by mass with respect to the epoxy resin (A). By making content into such a range, a film state becomes favorable (a film tack property is reduced) and film brittleness can also be suppressed.
  • the aluminum nitride filler (D) contained in the composition for a highly heat conductive film adhesive of the present invention contributes to increasing the heat conductivity of the film adhesive and reducing the linear expansion coefficient. If the value of the coefficient of linear expansion is high, the difference in coefficient of linear expansion from the wiring board becomes large, so that the effect of suppressing stress with these adherends is low, which leads to generation of package cracks.
  • the thermal resistance at the interface with resin tends to increase. Also. Since the reactivity with water is high, the surface is hydrolyzed by contact with water in a powder state, and ammonia is easily generated. This ammonia becomes ammonium ion, which easily corrodes the copper material during a reliability test such as bias HAST under high temperature and high humidity of the semiconductor package. Therefore, in the present invention, the aluminum nitride filler (D) is preferably surface-modified.
  • the surface modification method of aluminum nitride a method in which an aluminum oxide oxide layer is provided on the surface layer to improve water resistance, and surface treatment with phosphoric acid or a phosphoric acid compound is performed to improve affinity with the resin is preferable.
  • Phosphoric acid used in the surface treatment is orthophosphoric acid (H 3 PO 4 ), pyrophosphoric acid (H 4 P 2 O 7 ), metaphosphoric acid ((HPO 3 ) n, n is an integer representing the degree of condensation) or These metal salts are mentioned.
  • the phosphoric acid compound include organic phosphoric acids such as alkylphosphonic acid, arylphosphonic acid, alkylphosphoric acid, and arylphosphoric acid (for example, methylphosphonic acid, ethylphosphonic acid, hexylphosphonic acid, vinylphosphonic acid, phenylphosphonic acid, methylphosphoric acid, Ethyl phosphoric acid, hexyl phosphoric acid).
  • ion trapping agent ion trapping agent
  • the content of the aluminum nitride filler (D) is the total amount of the epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C), and the aluminum nitride filler (D). 30 to 60% by volume, more preferably 35 to 50% by volume. This is because the minimum melt viscosity value is controlled by the amount of aluminum nitride filler. If the blending amount is larger than the range, the minimum melt viscosity value becomes large, and when a semiconductor chip provided with this film adhesive is thermocompression bonded onto the wiring board, voids are likely to remain between the wiring board irregularities, and the film is fragile. Sexuality becomes stronger. When the blending amount is less than the range, the minimum melt viscosity value becomes small, and when the semiconductor chip provided with the film-like adhesive is mounted on the wiring substrate, the film-like adhesive tends to be poorly protruded.
  • the aluminum nitride filler (D) is preferably spherical from the viewpoint of high filling and fluidity.
  • the average particle size is preferably 0.01 to 5 ⁇ m. If the particle size is smaller than 0.01 ⁇ m, the filler tends to aggregate, causing unevenness during film production, and the resulting film thickness of the adhesive film may be poor. When the particle size is larger than 5 ⁇ m, when a thin film is produced with a coating machine such as a roll knife coater, the filler becomes a trigger, and streaks are likely to occur on the film surface.
  • the aluminum nitride (D) used in the present invention preferably has a Mohs hardness of 7-8.
  • Mohs hardness exceeds the upper limit, the wear rate of the processing blade by the film adhesive increases.
  • the Mohs hardness is a 10-stage Mohs hardness tester, which is rubbed in order from a mineral having a lower hardness to the measured object, to determine whether the measured object is damaged or not. Is a value determined.
  • the average particle diameter means a particle diameter when 50% accumulation is assumed when the total particle volume is 100% in the particle size distribution, and laser diffraction / scattering method (measuring condition: dispersion medium- (Sodium hexametaphosphate, laser wavelength: 780 nm, measuring device: Microtrac MT3300EX), and can be obtained from the cumulative curve of the volume fraction of the particle size distribution.
  • the term “spherical” refers to a true sphere or a substantially true sphere with roundness substantially without corners.
  • a powdered aluminum nitride filler and, if necessary, a silane coupling agent, phosphoric acid, phosphoric acid compound or surfactant are directly blended (Integral blend method), or a slurry-like aluminum nitride filler in which an aluminum nitride filler treated with a surface treatment agent such as a silane coupling agent, phosphoric acid or phosphoric acid compound or a surfactant is dispersed in an organic solvent
  • a blending method can be used.
  • the surface-treated aluminum nitride filler dispersion liquid dispersed in a smaller organic solvent is mixed with a resin component such as an epoxy resin, an epoxy resin curing agent, and a polymer, so that the aluminum nitride filler has a small particle size. Even if it exists, it can disperse
  • Silane coupling agents are those in which at least one hydrolyzable group such as an alkoxy group or an aryloxy group is bonded to a silicon atom, and in addition, an alkyl group, an alkenyl group, an alkenyl group, or an aryl group is bonded. May be.
  • the alkyl group is preferably an amino group, an alkoxy group, an epoxy group, or a (meth) acryloyloxy group substituted, and an amino group (preferably a phenylamino group), an alkoxy group (preferably a glycidyloxy group), or a (meth) acryloyl group. Those substituted with an oxy group are more preferred.
  • silane coupling agent examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 3-glycidyloxypropylmethyldimethoxy.
  • Silane 3-glycidyloxypropylmethyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N-phenyl-3-aminopropyltri Methoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, - such as methacryloyl Oki triethoxysilane and the like.
  • the surfactant may be anionic, cationic or nonionic, and may be a polymer compound.
  • an anionic surfactant is preferable, and a phosphate ester-based surfactant is more preferable.
  • a phosphate ester surfactant a phosphate ester represented by the following general formula (1) is preferable.
  • R 1 represents an alkyl group, an alkenyl group or an aryl group
  • L 1 represents an alkylene group
  • m represents an integer of 0 to 20
  • n represents 1 or 2.
  • the number of carbon atoms of the alkyl group in R 1 is preferably 1 to 20, more preferably 8 to 20, and still more preferably 8 to 18, for example, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, Examples include undecyl, dodecyl, hexadecyl, and octadecyl. Decyl, undecyl, and dodecyl are preferable, and undecyl is particularly preferable.
  • the carbon number of the alkenyl group in R 1 is preferably 2-20, more preferably 8-20, still more preferably 8-18, and examples thereof include allyl and oleyl.
  • the number of carbon atoms of the aryl group in R 1 is preferably 6-20, more preferably 6-20, still more preferably 6-18, and examples thereof include phenyl and nonylphenyl.
  • the number of carbon atoms of the alkyl group in L 1 is preferably 2 or 3, more preferably 2, and examples thereof include ethylene and propylene.
  • m is preferably an integer of 0 to 10.
  • the phosphate ester represented by the general formula (1) may be a mixture of n and 1;
  • phosphoric acid ester represented by the general formula (1) those commercially available as the phosphanol series manufactured by Toho Chemical Co., Ltd. can be used.
  • the silane coupling agent and the surfactant are preferably contained in an amount of 0.1 to 5.0% by mass with respect to the aluminum nitride filler (D).
  • the content of the silane coupling agent or the surfactant is less than the above lower limit, the aluminum nitride filler (D) is likely to aggregate and the appearance of the film surface is deteriorated.
  • excess silane coupling agent and surfactant remaining in the system volatilize in the semiconductor assembly heating process (for example, reflow process), causing peeling at the bonding interface.
  • the composition for a film adhesive of the present invention includes: Additives such as ion trapping agents (ion scavengers), curing catalysts, viscosity modifiers, antioxidants, flame retardants, colorants, stress relaxation agents such as butadiene rubbers and silicone rubbers, etc., as long as the effects of the invention are not impaired. May further be contained.
  • Additives such as ion trapping agents (ion scavengers), curing catalysts, viscosity modifiers, antioxidants, flame retardants, colorants, stress relaxation agents such as butadiene rubbers and silicone rubbers, etc.
  • an ion trapping agent for the purpose of capturing ammonium ions generated by hydrolysis of aluminum nitride with water.
  • the ion trapping agent include an inorganic ion trapping agent containing a triazine thiol compound, a zirconium compound, an antimony bismuth compound, and a magnesium aluminum compound.
  • the ion trapping agent is more preferably used in an amount of 1.0 to 3.0% by mass with respect to the aluminum nitride filler (D).
  • the ammonium ion concentration is preferably 80 ppm or less, and more preferably 70 ppm or less, in the measurement condition of the discharged water electrical conductivity. If the ammonium ion concentration exceeds the above upper limit, the concentration of ammonium ions and other ionic impurities increases, and the circuit member is easily corroded during the reliability test.
  • a curing catalyst examples include a phosphorus-boron type curing catalyst, a triphenylphosphine type curing catalyst, an imidazole type curing catalyst, and an amine type curing catalyst.
  • a phosphorus-boron type curing catalyst and a triphenylphosphine type curing catalyst are preferable.
  • boron type curing catalysts are preferred.
  • the triphenylphosphine type curing catalyst include triarylphosphine such as triphenylphosphine and tri-p-tolylphosphine, and are preferable.
  • Examples of phosphorus-boron type curing catalysts include tetraphenylphosphonium tetraphenylborate (trade name; TPP-K), tetraphenylphosphonium tetra-p-triborate (trade name; TPP-MK), and triphenylphosphine triphenylborane (trade name).
  • a phosphorus-boron curing accelerator such as TPP-S) (all manufactured by Hokuko Chemical Co., Ltd.).
  • TPP-S tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium tetra-p-triborate are preferable from the viewpoint of excellent storage stability at room temperature because of excellent latency.
  • the curing catalyst is preferably contained in an amount of 0.1 to 5.0% by mass with respect to the epoxy resin curing agent (B).
  • the composition for a highly heat conductive film adhesive of the present invention is applied onto one surface of a release-treated base film.
  • the release-treated base film may be any film that functions as a cover film for the obtained film adhesive, and any known film can be appropriately employed.
  • release-treated polypropylene (PP), release-treated polyethylene (PE), and release-treated polyethylene terephthalate (PET) may be mentioned.
  • a coating method a known method can be appropriately employed, and examples thereof include a method using a roll knife coater, a gravure coater, a die coater, a reverse coater and the like.
  • the film-like adhesive of the present invention preferably has a thickness of 5 to 200 ⁇ m, and more preferably 5 to 40 ⁇ m from the viewpoint that the unevenness on the surface of the wiring board or semiconductor chip can be more fully embedded. . If the thickness is less than the above lower limit, unevenness on the surface of the wiring board and the semiconductor chip cannot be embedded sufficiently, and sufficient adhesion tends to be not ensured. On the other hand, if the upper limit is exceeded, the organic solvent is removed during production. This makes it difficult to increase the amount of residual solvent and to increase the film tackiness.
  • FIG. 1 to FIG. 7 are schematic longitudinal sectional views showing a preferred embodiment of each step of the manufacturing method of the semiconductor package of the present invention.
  • the film-like shape of the present invention is formed on the back surface of a semiconductor wafer 1 having at least one semiconductor circuit formed on the front surface.
  • the adhesive is thermocompression-bonded to provide the adhesive layer 2, and then the semiconductor wafer 1 and the dicing tape 3 are provided via the adhesive layer 2.
  • a product in which the adhesive layer 2 and the dicing tape 3 are integrated may be thermocompression bonded at a time.
  • the semiconductor wafer 1 a semiconductor wafer having at least one semiconductor circuit formed on the surface can be used as appropriate, and examples thereof include a silicon wafer, a SiC wafer, and a GaS wafer.
  • the high thermal conductive film adhesive of the present invention may be used alone as one layer, or two or more layers may be laminated.
  • a method of providing such an adhesive layer 2 on the back surface of the wafer 1 a method capable of laminating the film adhesive on the back surface of the semiconductor wafer 1 can be appropriately employed.
  • a method of sequentially laminating the film adhesive until the desired thickness is achieved, or laminating the film adhesive to a desired thickness in advance examples include bonding to the back surface of the semiconductor wafer 1 after the process.
  • the semiconductor wafer 5 with the adhesive layer including the semiconductor wafer 1 and the adhesive layer 2 is obtained by simultaneously dicing the semiconductor wafer 1 and the adhesive layer 2.
  • the dicing tape 3 A well-known dicing tape can be used suitably.
  • the apparatus used for dicing is not particularly limited, and a known dicing apparatus can be used as appropriate.
  • the dicing tape 3 is detached from the adhesive layer 2, and the semiconductor chip 5 with the adhesive layer and the wiring substrate 6 are thermocompression bonded via the adhesive layer 2.
  • the semiconductor chip 4 with an adhesive layer is mounted on the wiring board 5.
  • a board having a semiconductor circuit formed on the surface can be used as appropriate.
  • a printed circuit board (PCB) various lead frames, and electronic components such as a resistance element and a capacitor are mounted on the board surface.
  • the substrate which was made is mentioned.
  • the method for mounting the semiconductor chip 5 with the adhesive layer on the wiring board 6 is not particularly limited, and the adhesive chip 2 is used to attach the semiconductor chip 5 with the adhesive layer to the wiring board 6 or the surface of the wiring board 6.
  • a conventional method capable of being bonded to the electronic component mounted thereon can be appropriately employed.
  • a conventionally known heating method such as a method using a mounting technique using a flip chip bonder having a heating function from the upper part, a method using a die bonder having a heating function only from the lower part, a method using a laminator, etc. And a pressurizing method.
  • the unevenness on the wiring substrate 5 caused by the electronic component is Since the film-like adhesive can be followed, the semiconductor chip 4 and the wiring board 6 can be brought into close contact and fixed.
  • thermosetting is not particularly limited as long as it is equal to or higher than the thermosetting start temperature of the film-like adhesive of the present invention, and varies depending on the type of resin used. From 180 to 180 ° C. is preferable, and from the viewpoint that curing at higher temperature can be performed in a short time, 140 to 180 ° C. is more preferable. If the temperature is lower than the thermosetting start temperature, thermosetting does not proceed sufficiently, and the strength of the adhesive layer 2 tends to decrease. On the other hand, if the upper limit is exceeded, the epoxy resin in the film adhesive during the curing process , Curing agents, additives, etc. tend to volatilize and tend to foam.
  • the curing treatment time is preferably 10 to 120 minutes, for example.
  • the film-like adhesive is thermally cured at a high temperature to obtain a semiconductor package in which the wiring substrate 6 and the semiconductor chip 4 are firmly bonded without generating voids even when cured at a high temperature. be able to.
  • connection method is not particularly limited, and a conventionally known method such as a wire bonding method, a TAB (Tape Automated Bonding) method, or the like can be appropriately employed.
  • a plurality of semiconductor chips 4 can be laminated by thermocompression-bonding and thermosetting another semiconductor chip 4 on the surface of the mounted semiconductor chip 4 and again connecting to the wiring substrate 6 by a wire bonding method.
  • a wire bonding method for example, as shown in FIG. 5, there are a method of stacking semiconductor chips while shifting, or a method of stacking while bonding wires 7 are buried by thickening the second adhesive layer 2 as shown in FIG.
  • the sealing resin 8 is not particularly limited, and a known sealing resin that can be used for manufacturing a semiconductor package can be used as appropriate. Moreover, it does not restrict
  • an adhesive layer 2 that is excellent in adhesion to an adherend, has a sufficiently low wear rate of a processing blade, and does not corrode a copper semiconductor member.
  • the heat generated on the surface of the semiconductor chip 4 can be efficiently released to the outside of the semiconductor package 9.
  • melt viscosity, thermal conductivity, extracted water electrical conductivity, blade wear rate, and corrosive evaluation were performed by the following methods.
  • the film-like adhesives obtained in each Example and Comparative Example were used as dummy silicon wafers at a temperature of 70 ° C. and a pressure of 0.3 MPa using a manual laminator (trade name: FM-114, manufactured by Technovision).
  • a manual laminator (trade name: FM-114, manufactured by Technovision)
  • the glass substrate After adhering to one surface of a glass substrate (10 ⁇ 10 cm, thickness 50 ⁇ m), the glass substrate as the dummy silicon wafer of the film adhesive at room temperature and pressure 0.3 MPa using the same manual laminator
  • a dicing tape (trade name: K-13, manufactured by Furukawa Electric Co., Ltd.) and a dicing frame (trade name: DTF2-8-1H001, manufactured by DISCO) were adhered to the opposite surface.
  • a dicing device [trade name: DFD-6340, manufactured by Z1: NBC-ZH2050 (27HEDD), manufactured by DISCO / Z2: NBC-ZH127F-SE (BC), manufactured by DISCO]) was installed.
  • the glass chip which is a dummy semiconductor chip was obtained by dicing so that it may become a size of 10 mm x 10 mm using DISCO].
  • the glass chip was mounted on a wiring board (FR) under the conditions of a temperature of 120 ° C., a pressure of 0.1 MPa (load: 1000 gf), and a time of 1.0 seconds using a die bonder [trade name: DB-800, manufactured by Hitachi High-Technologies Corporation] -4 substrate, thickness 200 ⁇ m).
  • a die bonder [trade name: DB-800, manufactured by Hitachi High-Technologies Corporation] -4 substrate, thickness 200 ⁇ m).
  • the state in the film adhesive after thermocompression bonding was observed from the back surface of the glass substrate. Void evaluation was evaluated according to the following evaluation criteria.
  • the obtained film adhesive was cut into square pieces with a side of 50 mm or more, the samples cut so that the thickness was 5 mm or more were stacked, placed on a disk-shaped mold with a diameter of 50 mm and a thickness of 5 mm, and a compression press Using a molding machine, the film-like adhesive is thermally cured by heating at a temperature of 150 ° C. and a pressure of 2 MPa for 10 minutes and then further heated in a dryer at a temperature of 180 ° C. for 1 hour. A disc-shaped test piece having a thickness of 5 mm was obtained.
  • thermal conductivity (W / m ⁇ K) was measured by a heat flow meter method (conforming to JIS-A1412) using a thermal conductivity measuring device (trade name: HC-110, manufactured by Eihiro Seiki Co., Ltd.). was measured.
  • the obtained film adhesive was attached to a dummy silicon wafer (8 inch size, thickness 100 ⁇ m) using a manual laminator (trade name: FM-114, manufactured by Technovision) at a temperature of 70 ° C. and a pressure of 0.3 MPa.
  • a manual laminator (trade name: FM-114, manufactured by Technovision) at a temperature of 70 ° C. and a pressure of 0.3 MPa.
  • a dicing tape (trade name: K-13, manufactured by Furukawa Electric Co., Ltd.) and a dicing frame on the side opposite to the dummy silicon wafer of the film adhesive at room temperature and a pressure of 0.3 MPa.
  • DTF2-8-1H001 manufactured by DISCO
  • a dicing machine (trade name) in which a biaxial dicing blade (Z1: NBC-ZH2030-SE (DD), manufactured by DISCO / Z2: NBC-ZH127F-SE (BB), manufactured by DISCO)) was installed.
  • Z1 NBC-ZH2030-SE (DD), manufactured by DISCO / Z2: NBC-ZH127F-SE (BB), manufactured by DISCO)
  • DFD-6340 manufactured by DISCO Ltd.
  • the semiconductor chip with a film-like adhesive under the conditions of a die bonder [trade name: DB-800, manufactured by Hitachi High-Technologies Corporation] at a temperature of 120 ° C., a pressure of 0.1 MPa (load of 1000 gf), and a time of 1.0 second was mounted on a lead frame substrate [material: 42 Arloy metal, thickness: 125 ⁇ m, manufactured by Toppan Printing Co., Ltd.] and heated at 150 ° C. for 1 hour to thermally cure the film adhesive.
  • the semiconductor chip and the lead frame substrate were made of copper wire [trade name: EX-1, 18 um ⁇ , Nippon Steel Material] at a stage temperature of 200 ° C. Manufactured by Co., Ltd.]. Furthermore, it mounted so that the said semiconductor chip with a film adhesive might be piled up on the semiconductor chip mounted previously, and the film adhesive was thermoset by heating at 150 degreeC for 1 hour.
  • these semiconductor chips are sealed with a molding agent (trade name: KE-3000F5-2, manufactured by Kyocera Corporation) in a molding apparatus (trade name: Y1E, manufactured by TOWA), and the temperature is set to 5 at 180 ° C.
  • the semiconductor package sample was obtained by performing heat treatment for a time to cure the molding agent.
  • the obtained film adhesive was attached to a dummy silicon wafer (8 inch size, thickness 100 ⁇ m) using a manual laminator (trade name: FM-114, manufactured by Technovision) at a temperature of 70 ° C. and a pressure of 0.3 MPa. Then, using the same manual laminator, dicing tape (trade name: G-11, manufactured by Lintec Co., Ltd.) and dicing frame on the side opposite to the dummy silicon wafer of the film adhesive at room temperature and pressure of 0.3 MPa [Product name: DTF2-8-1H001, manufactured by DISCO] was bonded to obtain a test piece.
  • a manual laminator trade name: FM-114, manufactured by Technovision
  • a dicing machine (trade name) in which a biaxial dicing blade (Z1: NBC-ZH2030-SE (DD), manufactured by DISCO / Z2: NBC-ZH127F-SE (BB), manufactured by DISCO)) was installed.
  • DFD-6340 manufactured by DISCO Co., Ltd.] to carry out dicing to 1.0 ⁇ 1.0 mm size.
  • Example 1 Novolac type phenol resin [trade name: PS-4271, mass average molecular weight: 400, softening point: 70 ° C., solid, hydroxyl group equivalent: 105 g / eq, manufactured by Gunei Chemical Co., Ltd.] 29 parts by mass, bisphenol A type epoxy resin [Product name: YD-128, mass average molecular weight: 400, softening point: 25 ° C.
  • the obtained mixed varnish was applied onto a release-treated polyethylene terephthalate film (PET film) having a thickness of 38 ⁇ m, dried by heating (held at 130 ° C. for 10 minutes), and a film adhesive having a thickness of 20 ⁇ m.
  • PET film polyethylene terephthalate film
  • An agent was obtained.
  • the obtained film adhesive was subjected to melt viscosity and thermal conductivity, extracted water electrical conductivity, corrosion evaluation, and blade wear evaluation. The obtained results are shown in Table 1 together with the composition of the film adhesive.
  • Example 2 Epoxy silane coupling agent [trade name: S-510, 3-glycidyloxypropyltrimethoxysilane, JNC Corporation] Phosphate ester surfactant [trade name; Phosphanol RS- 710, manufactured by Toho Chemical Co., Ltd.], 3 parts by weight of phosphoric acid-resistant aluminum nitride [trade name: HF-01A, average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / m ⁇ K, ( Made by Tokuyama Co., Ltd.)) Water resistant untreated aluminum nitride filler in place of 273 parts by mass [trade name: HF-01, average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / (m ⁇ K), ] Tokuyama] A film adhesive composition and a film adhesive were obtained in the same manner as in Example 1 except that 273 parts by mass were used.
  • Example 3 Water-resistant untreated aluminum nitride filler [trade name: HF-01, average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / m ⁇ K, manufactured by Tokuyama Corporation] Phosphorus as aluminum nitride instead of 273 parts by mass Except for using 273 parts by mass of acid-resistant aluminum nitride (trade name: HF-01A, average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / (m ⁇ K), manufactured by Tokuyama Corporation) In the same manner as in Example 2, a composition for film adhesive and a film adhesive were obtained.
  • HF-01A average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / (m ⁇ K), manufactured by Tokuyama Corporation
  • Example 4 Phosphate-treated water-resistant aluminum nitride [trade name: HF-01A, average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / m ⁇ K, manufactured by Tokuyama Corporation] 283 parts by mass, and ion trapping agent [Commercial name: IXE-6107, bismuth-zirconium-based, manufactured by Toagosei Co., Ltd.] A film adhesive composition and a film adhesive in the same manner as in Example 3 except that 4.3 parts by mass were used. Got.
  • Example 5 Phosphate-treated water-resistant aluminum nitride [trade name: HF-01A, average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / m ⁇ K, manufactured by Tokuyama Corporation] 283 parts by mass, and ion trapping agent [Product Name: IXE-100, zirconium-based, manufactured by Toagosei Co., Ltd.] A film adhesive composition and a film adhesive were obtained in the same manner as in Example 3 except that 4.3 parts by mass were used. It was.
  • Example 6 490 parts by mass of phosphoric acid-treated water-resistant aluminum nitride [trade name: HF-01A, average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / m ⁇ K, manufactured by Tokuyama Corporation], and ion trapping agent [Product Name: IXE-100, Zirconium, manufactured by Toagosei Co., Ltd.]
  • phosphoric acid-treated water-resistant aluminum nitride trade name: HF-01A, average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / m ⁇ K, manufactured by Tokuyama Corporation
  • ion trapping agent Product Name: IXE-100, Zirconium, manufactured by Toagosei Co., Ltd.
  • Example 7 169 parts by mass of phosphoric acid-treated water-resistant aluminum nitride [trade name: HF-01A, average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / m ⁇ K, manufactured by Tokuyama Corporation], and ion trapping agent [Product Name: IXE-100, zirconium-based, manufactured by Toagosei Co., Ltd.]
  • phosphoric acid-treated water-resistant aluminum nitride trade name: HF-01A, average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / m ⁇ K, manufactured by Tokuyama Corporation
  • ion trapping agent Product Name: IXE-100, zirconium-based, manufactured by Toagosei Co., Ltd.
  • Example 8 134 parts by mass of phosphoric acid-treated water-resistant aluminum nitride [trade name: HF-01A, average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / m ⁇ K, manufactured by Tokuyama Corporation], and ion trapping agent [Product Name: IXE-100, Zirconium, manufactured by Toagosei Co., Ltd.]
  • HF-01A phosphoric acid-treated water-resistant aluminum nitride
  • ion trapping agent Product Name: IXE-100, Zirconium, manufactured by Toagosei Co., Ltd.
  • Example 1 Phosphoric acid-resistant treated aluminum nitride (trade name: HF-01A, average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / m ⁇ K, manufactured by Tokuyama Corporation)
  • Example 1 except that 273 parts by mass of aluminum filler [trade name: HF-01, average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / (m ⁇ K), manufactured by Tokuyama Corporation] was used.
  • a composition for film adhesive and a film adhesive were obtained.
  • Example 2 Phosphate-resistant aluminum nitride [trade name: HF-01A, average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / m ⁇ K, manufactured by Tokuyama Corporation] 273 parts by mass of spherical alumina filler [ Product name: AX3-15R, average particle size 3.0 ⁇ m, Mohs hardness 9, thermal conductivity 36 W / (m ⁇ K), manufactured by Nippon Steel Materials Co., Ltd.] Example 1 except that 453 parts by mass were used Similarly, a composition for film adhesive and a film adhesive were obtained.
  • Comparative Example 4 79 parts by mass of phosphoric acid-treated water-resistant aluminum nitride (trade name: HF-01A, average particle size 1.1 ⁇ m, Mohs hardness 8, thermal conductivity 200 W / m ⁇ K, manufactured by Tokuyama Corporation), and ion trapping agent [Product Name: IXE-100, Zirconium, manufactured by Toagosei Co., Ltd.] A film adhesive composition and a film adhesive were obtained in the same manner as in Example 8 except that 1.2 parts by mass was used. .
  • each contains an epoxy resin, an epoxy resin curing agent, a phenoxy resin, and an aluminum nitride filler, and the content of the aluminum nitride filler is equal to the total amount of these resins and the filler. 30% to 60% by volume, satisfying all of the properties of the film adhesive specified in the present invention, while maintaining high thermal conductivity, the generation of voids is suppressed, and corrosion resistance and blade friction resistance are maintained. Excellent.
  • Comparative Example 1 compared with Examples 1 and 2, in Comparative Example 1, the value of the extracted water electrical conductivity was high and the corrosivity was inferior. This is presumed to be a result of the difference between the combination of the surface treatment agent and aluminum nitride having a large effect on the amount of ammonium ions generated during the bias HAST test.
  • Comparative Examples 2 and 3 using spherical alumina or boron nitride without using an aluminum nitride filler spherical alumina is used even though all of the characteristics of the film adhesive specified in the present invention are satisfied.
  • the blade friction was inferior.
  • Comparative Example 3 using boron nitride voids were generated. This is presumed to be due to the fact that boron nitride has a scaly shape, so that the melt viscosity after blending into the resin binder is likely to increase as compared to the spherical shape.
  • Comparative Example 4 in which the content of the aluminum nitride filler relative to the total amount of the epoxy resin, the epoxy resin curing agent, the phenoxy resin, and the aluminum nitride filler was less than 30% by volume, the minimum melt viscosity and the thermal conductivity were low.
  • the content of the aluminum nitride filler exceeds 60% by volume, the minimum melt viscosity and the electrical conductivity of the extracted water are high, voids are generated, and the corrosivity is also inferior.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Die Bonding (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition adhésive de type film contenant une résine époxyde, un agent de durcissement de résine époxyde, une résine phénoxy et une charge de nitrure d'aluminium, la teneur de la charge de nitrure d'aluminium étant de 30 à 60 % par rapport à la quantité totale de la résine époxyde, de l'agent de durcissement de résine époxyde, de la résine phénoxy et de la charge de nitrure d'aluminium, lorsque l'adhésif de type film obtenu par la composition adhésive de type film est chauffé à partir de 25 °C à une vitesse d'élévation de température de 5 °C/min, une viscosité à l'état fondu minimale dans la plage de 200 à 10 000 Pa∙s est atteinte à 80 °C ou plus, un corps durci présentant une conductivité thermique de 1,0 W/m•K ou plus est obtenu après durcissement, et la conductivité électrique de l'eau extraite extraite dans l'eau pure à 121 °C pendant 20 heures après durcissement est de 50 µS/cm ou plus. L'invention concerne également un adhésif de type feuille ; un procédé de production d'adhésif de type feuille ; un emballage de semi-conducteur, et un procédé de production associé.
PCT/JP2016/089006 2016-03-15 2016-12-27 Composition adhésive de type film, adhésif de type film, procédé de production d'adhésif de type film, emballage de semi-conducteur utilisant l'adhésif de type film, et procédé de production associé WO2017158994A1 (fr)

Priority Applications (3)

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JP2017518584A JP6868555B2 (ja) 2016-03-15 2016-12-27 フィルム状接着剤用組成物、フィルム状接着剤、フィルム状接着剤の製造方法、フィルム状接着剤を用いた半導体パッケージおよびその製造方法
KR1020177022011A KR102042516B1 (ko) 2016-03-15 2016-12-27 필름 형상 접착제용 조성물, 필름 형상 접착제, 필름 형상 접착제의 제조 방법, 필름 형상 접착제를 이용한 반도체 패키지 및 그 제조 방법
CN201680017697.0A CN107406742B (zh) 2016-03-15 2016-12-27 膜状接合剂用组合物、膜状接合剂及制造方法、使用膜状接合剂的半导体封装及制造方法

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JP2016051630 2016-03-15
JP2016-051630 2016-03-15

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WO2017158994A1 true WO2017158994A1 (fr) 2017-09-21

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JP (1) JP6868555B2 (fr)
KR (1) KR102042516B1 (fr)
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WO2022201687A1 (fr) * 2021-03-26 2022-09-29 古河電気工業株式会社 Film de fixation de puce de découpage en dés, son procédé de production, boîtier de semi-conducteur et son procédé de production
WO2023026584A1 (fr) 2021-08-23 2023-03-02 古河電気工業株式会社 Agent adhésif de type film et composant électronique l'utilisant ainsi que son procédé de production
WO2023112685A1 (fr) 2021-12-16 2023-06-22 古河電気工業株式会社 Feuille intégrée de couche substrat-adhésif pour dispositif flexible, et procédé de production de dispositif flexible
WO2023136017A1 (fr) 2022-01-13 2023-07-20 古河電気工業株式会社 Composition de résine pour dispositif souple, adhésif de type film pour dispositif souple, feuille adhésive pour dispositif souple et procédé de fabrication de dispositif souple
WO2023210427A1 (fr) 2022-04-28 2023-11-02 古河電気工業株式会社 Composition adhésive, adhésif de type film, boîtier de semi-conducteur utilisant un adhésif de type film et son procédé de fabrication

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KR102524818B1 (ko) * 2019-08-22 2023-04-25 후루카와 덴키 고교 가부시키가이샤 접착제용 조성물, 필름상 접착제 및 그의 제조 방법과, 필름상 접착제를 이용한 반도체 패키지 및 그의 제조 방법
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WO2018203527A1 (fr) * 2017-05-01 2018-11-08 古河電気工業株式会社 Film adhésif, ruban pour traiter une tranche de semi-conducteur, boîtier de semi-conducteur et procédé pour sa production
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WO2019216388A1 (fr) * 2018-05-10 2019-11-14 積水化学工業株式会社 Composition durcissable, matériau permettant la protection d'un élément à semiconducteurs, et dispositif à semiconducteurs
WO2021131523A1 (fr) * 2019-12-24 2021-07-01 富士フイルム株式会社 Agent adhésif pour endoscope, produit durci associé, endoscope et son procédé de fabrication
WO2021181748A1 (fr) * 2020-03-13 2021-09-16 古河電気工業株式会社 Film de fixation de matrice pour découpage en dés, boîtier de semi-conducteur utilisant un film de fixation de matrice pour découpage en dés, et procédé de fabrication de boîtier de semi-conducteur
JP2021145115A (ja) * 2020-03-13 2021-09-24 古河電気工業株式会社 ダイシングダイアタッチフィルム、並びに、ダイシングダイアタッチフィルムを用いた半導体パッケージ及びその製造方法
WO2022070503A1 (fr) 2020-09-29 2022-04-07 古河電気工業株式会社 Composition adhésive transparente, adhésif transparent de type film, procédé de fabrication d'un élément fourni par une couche adhésive transparente durcie, et composant électronique et procédé de fabrication associé
WO2022201687A1 (fr) * 2021-03-26 2022-09-29 古河電気工業株式会社 Film de fixation de puce de découpage en dés, son procédé de production, boîtier de semi-conducteur et son procédé de production
WO2023026584A1 (fr) 2021-08-23 2023-03-02 古河電気工業株式会社 Agent adhésif de type film et composant électronique l'utilisant ainsi que son procédé de production
WO2023112685A1 (fr) 2021-12-16 2023-06-22 古河電気工業株式会社 Feuille intégrée de couche substrat-adhésif pour dispositif flexible, et procédé de production de dispositif flexible
WO2023136017A1 (fr) 2022-01-13 2023-07-20 古河電気工業株式会社 Composition de résine pour dispositif souple, adhésif de type film pour dispositif souple, feuille adhésive pour dispositif souple et procédé de fabrication de dispositif souple
WO2023210427A1 (fr) 2022-04-28 2023-11-02 古河電気工業株式会社 Composition adhésive, adhésif de type film, boîtier de semi-conducteur utilisant un adhésif de type film et son procédé de fabrication

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TW201800521A (zh) 2018-01-01
JP6868555B2 (ja) 2021-05-12
TWI699419B (zh) 2020-07-21
KR102042516B1 (ko) 2019-11-13
CN107406742A (zh) 2017-11-28
JPWO2017158994A1 (ja) 2019-01-17
KR20170131355A (ko) 2017-11-29
CN107406742B (zh) 2020-12-29

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